The growth mechanism from pentatwinned (PTW) gold nanorods into truncated quasi-decahedral particles when a gold salt (HAuCl₄) is reduced by N, N-dimethylformamide (DMF) in the presence of poly(vinylpyrrolidone), was elucidated through a combination of different techniques, including transmission and scanning electron microscopy, high resolution TEM and selected area electron diffraction. Particles with intermediate shapes between the original pentatwinned Au nanorods, used as seeds, and the final quasi-decahedral particles were obtained by simply tuning the [HAuCl₄] to [seeds] ratio. From the thorough structural analysis of all the intermediate morphologies obtained, it was concluded that gradual morphology changes are related to the preferential growth of higher energy crystallographic facets. As a result of the particle growth and concomitant decreased anisotropy, a progressive blue-shift of the surface plasmon resonance bands of the nanoparticles was registered by vis-NIR extinction spectroscopy.